Plant unit and method for decomposing and purifying synthesis gas

ABSTRACT

An plant unit for fractionating and purifying synthesis gas is described, which is comprised of a device for partially condensing synthesis gas and a device for nitrogen washing, whereat the device for nitrogen washing is adjacent to the device for partial condensation.

Subject of the invention is a plant unit and a method for fractionating and purifying synthesis gas, allowing to perform two process steps in one single plant unit. In particular, the partial condensation of synthesis gas and the washing of synthesis gas by using liquid nitrogen are performed in one single plant unit, thereby yielding a number of purified gases or gas mixtures, which can be directly employed for further chemical syntheses.

For fractionating and purifying synthesis gases, it is known to use production plants, in which one generally can only separate one part of the synthesis gas, the latter of which has been produced by the partial oxidation of natural gas. In these known methods, carbon monoxide is separated by means of refrigeration engineering in one plant unit, which is known as device for partial gas condensation (1). Means of refrigeration engineering are also employed to obtain the synthesis gas required for ammonia production, whereat a plant unit is used, which is known as “nitrogen washing” (1). Both plant units have a completely different construction type. The only common feature of these two techniques of refrigeration engineering is to be found in the use of a multiway plate heat exchanger for cooling off and reheating the gas streams. Each of these methods requires a cooling device, which in a partial condensation unit in general can be realised by the expansion of carbon monoxide or hydrogen, whereat a unit for nitrogen washing requires liquid nitrogen.

In the present invention, two steps of purification are combined in a single method, whereat the crude synthesis gas is cooled off to cryogenic temperatures, in which the carbon monoxide can be separated from the synthesis gas. The remaining hydrogen is purified in a nitrogen washing column, followed by a subsequent, optional mixing with further nitrogen in order to be used for ammonia synthesis.

The advantages of the plant unit according to the invention in comparison to the prior art are mainly based thereupon, that

-   a) a heat exchange being much more efficient is realised in the     plate heat exchangers; -   b) a special cooling system in the form of an expander is not     required for the purification of carbon monoxide, whereby the     operating safety of the total system is improved; -   c) the reliability of gas supply is thereby improved, that—in case     of a reduced demand for either carbon monoxide or for ammonia     synthesis gas—the plant unit according to the invention allows to be     kept cool by the maintained purification of the other synthesis gas     and allows to be very quickly readjusted to a full production rate     of both synthesis gases; -   d) the plant unit according to the invention allows to be     constructed and erected in a much more economical manner than two     separate cryogenic systems.

Subject of the invention accordingly is a plant unit for the fractionation and purification of synthesis gas, which is comprised of a device for partially condensing synthesis gas and of a device for nitrogen washing, whereat the device for nitrogen washing is adjacent to the device for partial condensation.

The plant unit according to the invention is schematically depicted in FIG. 1. The composition of the plotted streams of matter is to bee seen in Table 1.

The plant unit according to the invention provides the following interconnected devices:

-   -   a heat exchanger A for cooling off the synthesis gas fed to the         plant unit     -   a separator B, which is connected to the heat exchanger A, for         fractionating the synthesis gas 2 into a gas fraction 4, mainly         consisting of hydrogen and carbon monoxide, and into a liquid         fraction 5, mainly consisting of carbon monoxide and methane;     -   a separator C for further fractionating the gas fraction 4         supplied from the separator B in order to produce a gas fraction         6 predominantly consisting of hydrogen and a liquid 7         predominantly consisting of carbon monoxide;     -   an evaporator D, in which the hydrogen being absorbed in the         liquid 7 is evaporated and by which the remaining liquid 8         mainly containing carbon monoxide can be fed to a distillation         column F;     -   a further evaporator E, in which the remaining, absorbed         hydrogen in the liquid fraction 5 of separator B is removed by         evaporation and by which the liquid 9 mainly containing carbon         monoxide and methane can be fed to the distillation column F;     -   a distillation column F for the separation of gaseous carbon         monoxide and for obtaining methane as a liquid depositing at the         bottom of the column; and     -   a washing column G for removing contaminations from the gas         fraction 6 being supplied from the separator C and mainly         containing hydrogen, whereat this purification is accomplished         by using liquid nitrogen and whereat the contaminations are used         as a burnable gas 12.

The heat exchanger A preferably is a multiway plate heat exchanger, in which the exchanger plates generally consist of aluminium. The heat exchanger A can receive a multiplicity of gas and liquid feed lines and is able to cool them off or to heat them to preset temperatures.

The synthesis gas 2 being supplied from the heat exchanger A to the plant unit according to the invention is fractionated in the separator B into a gas fraction 4 being rich in hydrogen and a liquid phase 5 being rich in carbon monoxide and methane. This separation is accomplished at a pressure of about 78 bar and a temperature of −171±10° C. The gas fraction 4 is further cooled off in the heat exchanger A and then fed to the separator C. The liquid 5 is decompressed to a pressure of about 6 bar and fed to the evaporator E.

The decompression evaporator C is a device, in which the hydrogen-rich gas 4, which is supplied from the separator B, is further fractionated, namely into a gas 6 predominantly consisting of hydrogen and into a liquid 7 predominantly consisting of carbon monoxide. This separation is performed at a pressure of about 78 bar and a temperature of −195±10° C. The gas 6 still being contaminated by carbon monoxide is fed to the bottom part of the washing column G. The liquid 7 is divided into two streams, one stream designated for further purification and the other stream containing excess carbon monoxide still containing hydrogen. It can also be used as a synthesis gas for generating products like methanol, which are produced from carbon monoxide and hydrogen.

The carbon monoxide 7 designated for further purification is decompressed to a pressure of about 6 bar and fed to the flash evaporator (decompression evaporator) D.

In the receptacle D, the hydrogen being absorbed in the carbon monoxide is evaporated by flash evaporation. It can then, after having passed through the heat exchanger A, be used as burnable gas 15. The flash evaporation is accomplished at a pressure of about 6 bar and a temperature of −195±10° C. The liquid 8, which is produced in this process, is fed to the distillation column F.

The liquid 5, which has been obtained in the separator B, is fed to the flash evaporator E, and the hydrogen being absorbed in the liquid carbon monoxide is evaporated and can then be discharged via the heat exchanger A and be used as a burnable gas. This flash evaporation is accomplished at a pressure of about 6 bar and a temperature of −171±10° C. The liquid 9 being obtained in the receptacle E is fed to the distillation column F.

The distillation column 11 serves to produce highly pure carbon monoxide having a purity of greater than 98% by volume. The distillation column is pressurised at a pressure of about 5 bar and in its upper portion provides temperatures of about −175° C. and in its bottom portion of about −155° C. Into this column, a mixture of carbon monoxide and methane from the flash evaporator E (9) and the liquid mainly consisting of carbon monoxide from the flash evaporator D have been introduced.

The distillation in this column F is accomplished by heating by means of a heat exchanger passed through by a synthesis gas of arbitrary composition or by means of a discharge located at the bottom of the column and receiving the liquid accumulating there, whereat this liquid can be reconducted into the distillation column after having passed though the heat exchanger A (not depicted by a figure). The gas accumulating in the upper part of the distillation column is nearly completely pure carbon monoxide, which is reconducted into the heat exchanger A. It is then available for syntheses, in which high-purity carbon monoxide is required.

The liquid precipitating at the bottom of the distillation column F is nearly pure liquid methane, which is decompressed to a pressure of about 1,3 bar and, after having passed through the heat exchanger A, is available as a burnable gas.

The washing column G serves to purify hydrogen by means of liquid nitrogen and to simultaneously generate a hydrogen/nitrogen mixture. The washing column is pressurised to a pressure of about 77 bar and exhibits a temperature of −185° C.+10° C. Nearly pure gaseous hydrogen from the flash evaporator C is introduced into the bottom part of the washing column via the conduit 6. Liquid nitrogen is introduced into the washing column, whereby in the washing column G, a mixture of hydrogen and nitrogen is produced, which has residual concentrations of carbon monoxide and argon of less than 5 ppm and 150 ppm, respectively. The product withdrawn at the upper portion of the washing column can then be mixed with further gaseous nitrogen and be adjusted to a molar proportion of hydrogen to nitrogen of about 3:1, in general to a molar proportion of 2,995, and be provided as a synthesis gas for ammonia synthesis via the heat exchanger A. At the bottom of the washing column G, a mixture of liquid carbon monoxide, argon and nitrogen is formed, which is decompressed to a pressure of 1,3 bar and used as a burnable gas via the heat exchanger A.

The liquid nitrogen employed in the washing column has a purity of 99,995% and is liquefied in the heat exchanger A and fed to the washing column G as a high pressure nitrogen gas. This form of nitrogen can also be comprised of several streams of nitrogen, which are fed to the washing column at different pressures. The mixture of the different streams of nitrogen can then be compressed by pumping to reach the required operating pressure.

The liquid nitrogen serves the aim to cool off the low pressure liquid streams at the bottom of the washing column G.

The plant unit according to the invention is a central part in the plant for the fractionation of synthesis gas, which is described in the German patent application 102 26 209.8 being filed at the same date. In this specification, the complete method for the fractionation of synthesis gas is described. Thereby, at first the carbon dioxide contained in the synthesis gas is separated. The remaining gas mixture, which predominantly consists of carbon monoxide and hydrogen, constitutes the stream of the synthesis gas 2, the fractionation of which has been described by employing the plant unit according to the invention.

REFERENCES

-   1. “Gas Production”, Ullman's Encyclopedia of Industrial Chemistry,     Vol. A12, VCH Verlagsgesellschaft mbH (1989).     List of Reference Numbers: -   A heat exchanger -   B separator -   C separator -   D decompression device -   E decompression device -   F device for distillation or rectification/fractionation -   G device for nitrogen washing -   1 nitrogen under increased pressure -   2 synthesis gas -   3 liquid nitrogen -   4 gas fraction, consisting of hydrogen, carbon monoxide and traces     of methane -   5 liquid fraction, consisting of carbon monoxide, methane and     hydrogen -   6 gas fraction, consisting of hydrogen and little carbon monoxide -   7 liquid fraction, consisting of carbon monoxide, little methane and     traces of hydrogen -   8 liquid fraction, consisting of carbon monoxide, little methane and     traces of hydrogen -   9 liquid fraction, consisting of carbon monoxide and methane -   10 liquid fraction, consisting of methane and little carbon monoxide -   11 liquid nitrogen -   12 liquid fraction, consisting of carbon monoxide, nitrogen,     hydrogen and little traces of argon -   13 gas fraction, consisting of carbon monoxide, little hydrogen and     little methane -   14 gas fraction, consisting of carbon monoxide -   15 gas fraction, consisting of carbon monoxide, nitrogen, hydrogen,     methane and traces of argon

16 gas fraction, consisting of hydrogen and nitrogen TABLE I Gas stream 1 2 3 4 5 6 7 8 Composition (% by volume) Methane 2.59 1.00 23.04 0.03 6.34 7.22 Carbon 19.94 16.46 64.16 4.81 82.04 91.43 monoxide Argon 0.10 0.07 0.42 0.01 0.40 0.45 Hydrogen 77.38 82.49 12.39 95.15 11.22 0.90 Nitrogen 99.99 99.99 Temp. 40 36 −195 −171 −171 −195 −195 −193 (° C.) Pressure 80 77 2 77 77 77 77 5.8 (bar abs) Vapor 1 1 0 1 0 1 0 0 portion Rate of 142 149 6 118 32 51 67 41 flow (t/h) Gas stream 9 10 11 12 13 14 15 16 Composition (% by volume) Methane 29.80 91.6 0.41 6.34 0.70 16.97 Carbon 69.23 7.66 69.00 82.04 98.14 46.89 2.57 monoxide ppm Argon 0.48 0.65 0.19 0.40 0.41 0.25 Hydrogen 0.48 13.31 11.22 0.75 16.69 74.97 Nitrogen 99.99 17.08 19.20 25.03 Temp. −178 −143 −185 −196 31 31 31 31 (° C.) Pressure 5.8 5.8 77 76 76 50 1.2 75 (bar abs) Vapor 0 0 0 0 1 1 1 1 portion Rate of 27 6.2 39 26 63 25 43 166 flow (t/h) 

1. Plant unit for the fractionation and purification of synthesis gas, characterised in that it provides a device for partially condensing synthesis gas and a device for nitrogen washing, whereat the device for nitrogen washing is adjacent to the device for partial condensation.
 2. Plant unit according to claim 1, characterised in that it comprises the following interconnected devices: a heat exchanger A for cooling off the synthesis gas fed to the plant unit a separator B, which is connected to the heat exchanger A, for fractionating the synthesis gas 2 into a gas fraction 4, mainly consisting of hydrogen and carbon monoxide, and into a liquid fraction 5, mainly consisting of carbon monoxide and methane; an evaporator C for further fractionating the gas fraction 4 supplied from the separator B in order to produce a gas fraction 6 predominantly consisting of hydrogen and a liquid 7 predominantly consisting of carbon monoxide; an evaporator D, in which the hydrogen being absorbed in the liquid 7 is evaporated and by which the remaining liquid 8 mainly containing carbon monoxide can be fed to a distillation column F; a further evaporator E, in which the remaining, absorbed hydrogen in the liquid fraction 5 of separator B is removed by evaporation and by which the liquid 9 mainly containing carbon monoxide and methane can be fed to the distillation column F; a distillation column F for the separation of gaseous carbon monoxide and for obtaining methane as a liquid depositing at the bottom of the column; and a washing column G for removing contaminations from the gas fraction 6 being supplied from the evaporator C and mainly consisting of hydrogen, whereat this purification is accomplished by using liquid nitrogen and whereat the contaminations are used as a burnable gas
 12. 3. Plant unit according to claim 1, characterised in that the heat exchanger A can receive a multiplicity of feed lines for gases and liquids and is able to cool them off or to heat them to preset temperatures.
 4. Plant unit according to claim 1, characterised in that the evaporators C, D and E are flash evaporators (decompression evaporators), by which the gas, which is dissolved in a liquid, can be removed.
 5. Plant unit according to claim 1, characterised in that the distillation column F provides a heat exchanger being passed through by a synthesis gas of arbitrary composition or a discharge being located at the bottom of the column and receiving the liquid accumulating there, whereat this liquid can be reconducted to the distillation column after having passed through the heat exchanger A.
 6. Plant unit according to claim 1, characterised in that the washing column G comprises feed lines for gaseous and liquid nitrogen.
 7. Method for fractionating and purifying synthesis gas in the plant unit of claim 1, characterised in that firstly a partial condensation of the synthesis gas and subsequently a washing by means of liquid nitrogen are performed.
 8. Method according to claim 7, characterised in that in the separator B, the separation of the synthesis gas 2 into a gas fraction 4, mainly consisting of hydrogen and carbon monoxide, and into a liquid fraction 5, mainly consisting of carbon monoxide and methane, is performed at a pressure of about 78 bar and a temperature of −171±10° C.
 9. Method according to claim 7, characterised in that in the evaporator C, the separation of the gas fraction 4 into a gas fraction 6 predominantly consisting of hydrogen and into a liquid 7 predominantly consisting of carbon monoxide is performed at a pressure of about 78 bar and a temperature of −195±10° C.
 10. Method according to claim 7, characterised in that in the evaporator D, the hydrogen being absorbed in the liquid 7 is evaporated at a pressure of 6 bar and a temperature of −195±10° C.
 11. Method according to claim 7, characterised in that in the evaporator E, the hydrogen being absorbed in the liquid 5 is evaporated at a pressure of 6 bar and a temperature of −171±10° C.
 12. Method according to claim 7 characterised in that the separation of the carbon monoxide in the distillation column F is performed under the employment of a pressure of about 5 bar, a temperature of about −175° C. at the column head and a temperature of about −155° C. at the bottom of the column.
 13. Method according to claim 7, characterised in that in the washing column G, the removal of contaminations from the gas fraction 6 mainly containing hydrogen is performed by employing liquid nitrogen, a column pressure of about 77 bar and a temperature of −185±10° C.
 14. Method according to claim 7 characterised in that the gas mixture withdrawn at the upper portion of the washing column is adjusted to a molar proportion of H₂/N₂ of about 3:1 by adding gaseous nitrogen. 